Several organo-gallium/indium chalcogenide complexes of copper(I), stabilized by trialkylphosphines, were isolated, structurally characterized by using single-crystal X-ray diffraction, and investigated in thermolysis experiments. The syntheses with [E(Me3Si)2] (E=S, Se) as a starting material and a chalcogen source involve the elimination of volatile silyl acetate, silyl ethers, and methane from copper(I) acetate, and Group 13 metal trimethyl compounds, respectively. Chalcogenide complexes, according to the general formulas [(R3PCu)4(MeM)4E6] (1-6) and [(R3PCu)6(MeM)4M4S13] (7-9; with R=alkyl and M=Ga, In), and mixed chalcogenide-phenylchalcogenolate complexes [(iPr3PCuEPh)3(MeGaE)4] (10, 11) were isolated. The heavy atom cores of 1-6 consist of an octahedron of chalcogen atoms, interpenetrated by a cube of metal atoms. Depending on the steric demand of the phosphine ligands, two constitutions are observed; the metal atoms of the same element either forming tetrahedra, or parallelograms, respectively. This constitutional isomerism is further investigated by quantum chemical calculations. Complexes 7-9 contain a central sulfur atom, surrounded by two interpenetrating tetrahedra of Group 13 metal atoms, an octahedron of copper atoms, and an icosahedron of twelve outer sulfur atoms; the heavy atom framework of 10 and 11 is a "cut-out" of this structure. Thermolysis experiments include thermogravimetry measurements and subsequent Rietveld phase analysis of the residues by using powder X-ray diffraction. The homologous compounds 1, 3, 4, and 6 yield the respective crystalline ternary semiconductor material CuME2 at temperatures below 300 °C. Partial release of Me3 M during the thermolysis process results in excess copper in the residue and therefore in small amounts of additional binary copper chalcogenide phases or metallic CuM alloys. Compound 8 produces nanocrystalline CuGaS2 at about 300 °C.

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